Arsenic removal from natural groundwater using ‘green rust’: Solid phase stability and contaminant fate

[Display omitted] •‘Green rust’ (GR) phases (e.g., carbonate, sulfate) can efficiently remove arsenic (As) species from natural groundwater.•Aging GRSO4 in natural groundwater led to anion exchange and re-structuring to form GRCO3 and then conversion to magnetite.•As adsorbed to GR surfaces can slow down the interlayer anion exchange of SO42− with CO32−.•Low temperature and adsorbed As increased GRSO4 long-term stability, inhibiting magnetite formation even after a year. Arsenic (As) contamination in groundwater remains a pressing global challenge. In this study, we evaluated the potential of green rust (GR), a redox-active iron phase frequently occurring in anoxic environments, to treat As contamination at a former wood preservation site. We performed long-term batch experiments by exposing synthetic GR sulfate (GRSO4) to As-free and As-spiked (6 mg L−1) natural groundwater at both 25 and 4 °C. At 25 °C, GRSO4 was metastable in As-free groundwater and transformed to GRCO3, and then fully to magnetite within 120 days; however, GRSO4 stability increased 7-fold by lowering the temperature to 4 °C, and 8-fold by adding As to the groundwater at 25 °C. Highest GRSO4 stability was observed when As was added to the groundwater at 4 °C. This stabilizing effect is explained by GR solubility being lowered by adsorbed As and/or lower temperatures, inhibiting partial GR dissolution required for transformation to GRCO3, and ultimately to magnetite. Despite these mineral transformations, all added As was removed from As-spiked samples within 120 days at 25 °C, while uptake was 2 times slower at 4 °C. Overall, we have successfully documented that GR is an important mineral substrate for As immobilization in anoxic subsurface environments.